Timothy N. Hunter

Adsorption of Submicrometer-Sized Cationic Sterically Stabilized Polystyrene Latex at the Air−Water Interface: Contact Angle Determination by Ellipsometry

Near-monodisperse, sterically stabilized cationic polystyrene latexes of either 122 or 310 nm diameter were prepared by aqueous emulsion polymerization using cheap, readily available reagents. At low pH, these latexes stabilized foams prepared by either hand-shaking or by using a foam column. SEM studies confirmed that the dried foam mainly comprised well-defined bilayers, which suggests that each air bubble is stabilized with a latex monolayer. Adsorption of the same latexes at the planar air-water interface was studied using the Langmuir-Blodgett trough technique. Surface pressure isotherms confirmed particle desorption from the interface on repeated compression of the latex monolayers. For the 122 nm latex at pH 2, ellipsometric analysis enabled a contact angle of approximately 43 degrees to be calculated from a simple two-layer model, which suggests that these particles have only moderate wettability. Similar results were obtained for the 310 nm latex, but the data were much less reliable in this case due to additional background particle scattering.

Measuring particle concentration in multiphase pipe flow using acoustic backscatter: generalization of the dual-frequency inversion method.

A technique that is an extension of an earlier approach for marine sediments is presented for determining the acoustic attenuation and backscattering coefficients of suspensions of particles of arbitrary materials of general engineering interest. It is necessary to know these coefficients (published values of which exist for quartz sand only) in order to implement an ultrasonic dual-frequency inversion method, in which the backscattered signals received by transducers operating at two frequencies in the megahertz range are used to determine the concentration profile in suspensions of solid particles in a carrier fluid. To demonstrate the application of this dual-frequency method to engineering flows, particle concentration profiles are calculated in turbulent, horizontal pipe flow. The observed trends in the measured attenuation and backscatter coefficients, which are compared to estimates based on the available quartz sand data, and the resulting concentration profiles, demonstrate that this method has potential for measuring the settling and segregation behavior of real suspensions and slurries in a range of applications, such as the nuclear and minerals processing industries, and is able to distinguish between homogeneous, heterogeneous, and bed-forming flow regimes.

Behavior of pH-sensitive core shell particles at the air-water interface

In this article, the adsorption of latex core-responsive polymer-shell nanoparticles at the air-water interface is investigated using a Langmuir trough. Phase transition isotherms are used to explore their responsive behavior at the interface as a function of changes in the pH of the subphase. By adjusting the pH of the water prior to particle deposition, we probe the effect of the stabilizing polymer wetting by the water subphase on the stability of these particles at the air-water interface. In addition, by initially compressing a stable film of adsorbed particles and then subsequently changing the pH of the subphase we study desorption of these particles into the water phase.

Organically modified clay with potassium copper hexacyanoferrate for enhanced Cs+ adsorption capacity and selective recovery by flotation

The selective capture of mobile radioactive nuclides, such as 137Cs+, is crucial to the clean-up and remediation of contaminated environments. While remediation remains a challenging task, the current study considers novel organo-clay composites containing potassium copper hexacyanoferrate (KCuHCF) as a viable option for large-scale clean-up. A three-step synthesis has been demonstrated whereby pristine montmorillonite clay was readily modified to incorporate KCuHCF nanoparticles for enhanced and selective Cs+ removal from aqueous environments. Alkyldiamine (DT) was used as an organic modifier to intercalate the clay and provided chelating sites to anchor copper onto the clay matrix, from which KCuHCF nanoparticles were subsequently grown in situ via the coordination of hexacyanoferrate precursors with the immobilized copper ions. The organo-clay–HCF composite particles exhibited a superior Cs+ adsorption capacity (qm = 206 mg g−1), twice that of the pristine clay. The enhanced performance also extended to high Cs+ selectivity in seawater, with the organo-clay–HCF composites demonstrating Cs+ selectivity values in excess of 105 mL g−1, two orders of magnitude greater than the pristine clay. Organo modification of the clay particles reduced the particle wettability, thus facilitating the separation of Cs-loaded composite particles from aqueous environments by collector-less flotation. Batch flotation experiments showed recovery efficiencies of the Cs-loaded composite particles of up to 90%, which was in great contrast to the low recovery of less than 15% for the Cs-loaded pristine montmorillonite. The current study provides a new concept for the treatment of contaminated aqueous environments.

Manufacture of poly(methyl methacrylate) microspheres using membrane emulsification

Accurate control of particle size at relatively narrow polydispersity remains a key challenge in the production of synthetic polymer particles at scale. A cross-flow membrane emulsification (XME) technique was used here in the preparation of poly(methyl methacrylate) microspheres at a 1–10 l h−1 scale, to demonstrate its application for such a manufacturing challenge. XME technology has previously been shown to provide good control over emulsion droplet sizes with careful choice of the operating conditions. We demonstrate here that, for an appropriate formulation, equivalent control can be gained for a precursor emulsion in a batch suspension polymerization process. We report here the influence of key parameters on the emulsification process; we also demonstrate the close correlation in size between the precursor emulsion and the final polymer particles. Two types of polymer particle were produced in this work: a solid microsphere and an oil-filled matrix microcapsule. This article is part of the themed issue ‘Soft interfacial materials: from fundamentals to formulation’.

Numerical and experimental analysis of the sedimentation of spherical colloidal suspensions under centrifugal force

Understanding the sedimentation behaviour of colloidal suspensions is crucial in determining their stability. Since sedimentation rates are often very slow, centrifugation is used to expedite sedimentation experiments. The effect of centrifugal acceleration on sedimentation behaviour is not fully understood. Furthermore, in sedimentation models, interparticle interactions are usually omitted by using the hard-sphere assumption. This work proposes a one-dimensional model for sedimentation using an effective maximum volume fraction, with an extension for sedimentation under centrifugal force. A numerical implementation of the model using an adaptive finite difference solver is described. Experiments with silica suspensions are carried out using an analytical centrifuge. The model is shown to be a good fit with experimental data for 480 nm spherical silica, with the effects of centrifugation at 705 rpm studied. A conversion of data to Earth gravity conditions is proposed, which is shown to recover Earth gravity sedimentation rates well. This work suggests that the effective maximum volume fraction accurately captures interparticle interactions and provides insights into the effect of centrifugation on sedimentation.

Development of a real-time acoustic backscatter system for solids concentration measurement during nuclear waste cleanup

The measurement of the concentration of solid particles in suspension without physical sampling is a necessary tool for the nuclear industry involved with cleanup of a significant quantity of legacy waste in the form of sludge. This paper presents the work of a project to develop acoustic instrumentation for the in-situ characterization of such sludge. The measurement principle and signal processing employed is presented along with the design of a custom acoustic instrument for deployment in nuclear and industrial environments. The paper presents experimental results demonstrating the ability of the technique for the online measurement of mass concentration in a suspension of glass power in water.

Facile synthesis of gold core-polymer shell responsive particles

The free adsorption of an end-functionalised weak polybase, poly dimethylaminoethyl methacrylate (pDMAEMA), on the surface of colloidal gold nanoparticles (AuNPs) as a route to produce a responsive core-shell nanoparticle is explored here. Optimal conditions for the physisorption of the polymeric chains onto the colloidal nanoparticles are explored. A dense coverage is facilitated by rapidly mixing the well solvated pH responsive homopolymer, at low pH, into a relatively poor solvent environment, at higher pH, containing a stable dispersion of charge-stabilised gold nanoparticles. The rapid pH change causes the polymer chains to concurrently collapse and adsorb onto the gold nanoparticles. In order to achieve sterically stable, monodisperse and responsive core shell nanoparticles, a crucial factor is the pH difference of the systems prior to their mixing. Once adsorbed, end-functional thiol groups on the adsorbed polymer chains can form more permanent covalent attachments with the core particles. Dynamic light scattering coupled with mobility data of pH titration experiments show that the core-shell particles exhibit a responsive character consistent with the observed potentiometric titration data of the polymer. The same particles demonstrate reversible aggregation when cycled between pH extremes. This is confirmed by shifts in the SPR peak of the corresponding UV-Vis absorption profile. The ease and flexibility of this strategy for core-shell particle production, coupled with the stability and responsiveness of the product, make this a promising colloidal coating mechanism.

Engineering properties of nuclear waste slurries

The type of particulate systems encountered in legacy nuclear waste slurries is highly complicated, with the aggregation and flow behaviour being at times very variable. However, deconstructing the complex overall slurry activity to singular particle-particle interactions can lead to a greater understanding of the mechanisms involved with particle aggregation, and so to predictions of their settling and flow in nuclear systems. Of particular importance to legacy waste is the role of salts in controlling the attraction of particles (and so in dictating the rheological properties of the system) as sludge may contain a variety of specific ions and generally have high ionic conductivity [1]. In this paper, particle-particle interactions are characterised using a number of complimentary methods, and their influence on resulting flow and bed compression is measured. The methods used to characterise the particle-particle interactions under various salt and pH conditions were electroacoustic analysis (zeta potential) and atomic force microscopy (AFM). Following on from the analysis of particle-particle properties, bulk sediment behaviour was investigated using shear and compressive yield stress measurements, vital parameters in dictating flow and dewatering performance, respectively. Together, these techniques enable the characterisation of a range of particulate systems that may be encountered in legacy wastes, and results point to a number of important factors that can help explain the observed variability in industrial slurry behaviour.

Synthesis and Physical Property Characterisation of Spheroidal and Cuboidal Nuclear Waste Simulant Dispersions

This study investigated dispersions analogous to highly active nuclear waste, formed from the reprocessing of Spent Nuclear Fuel (SNF). Non-radioactive simulants of spheroidal caesium phosphomolybdate (CPM) and cuboidal zirconium molybdate (ZM-a) were successfully synthesised; confirmed via Scanning Electron Microscopy (SEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy. In addition, a supplied ZM (ZM-b) with a rod-like/wheatsheaf morphology was also analysed along with titanium dioxide (TiO2). The simulants underwent thermal gravimetric analysis (TGA) and size analysis, where CPM was found to have a D50 value of 300 nm and a chemical formula of Cs3PMo12O40·13H2O, ZM-a a D50 value of 10 μm and a chemical formula of ZrMo2O7(OH)2·3H2O and ZM-b to have a D50 value of 14 μm and a chemical formula of ZrMo2O7(OH)2·4H2O. The synthesis of CPM was tracked via Ultraviolet-visible (UV-Vis) spectroscopy at both 25 °C and 50 °C, where the reaction was found to be first order with the rate constant highly temperature dependent. The morphology change from spheroidal CPM to cuboidal ZM-a was tracked via SEM, reporting to take 10 days. For the onward processing and immobilisation of these waste dispersions, centrifugal analysis was utilised to understand their settling behaviours, in both aqueous and 2 M nitric acid environments (mimicking current storage conditions). Spheroidal CPM was present in both conditions as agglomerated clusters, with relatively high settling rates. Conversely, the ZM were found to be stable in water, where their settling rate exponents were related to the morphology. In acid, the high effective electrolyte resulted in agglomeration and faster sedimentation.